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Special Issue "Frontiers in Metal-Catalysed Cross-Coupling Reactions for the Synthesis and Functionalisation of Heterocycles"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (31 December 2018)

Special Issue Editors

Guest Editor
Prof. Dr. Artur M. S. Silva

Department of Chemistry & QOPNA—Organic Chemistry, Natural Products and Food Stuffs, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal
Website | E-Mail
Interests: organic synthesis; organocatalysis; transition-metal catalysis; oxygen and nitrogen heterocyclic compounds; chemistry of natural products; green chemistry; microwave-assisted organic synthesis; ohmic heating-assisted organic synthesis
Guest Editor
Dr. Maria Manuel Marques

Chemistry Department, Faculty of Science and Technology - UNL, Caparica, Portugal
Website | E-Mail
Interests: organic synthesis; palladium-catalysed reactions; heterocyclic compounds; sustainable synthetic methods; medicinal chemistry; development of synthetic methods; carbohydrate chemistry

Special Issue Information

Dear Colleagues,

Transition metal-catalyzed cross-coupling reactions are of paramount importance in organic synthesis. Over the past 30 years, metal-catalyzed C−X (X = C, N, O, S, etc.) bond formation reactions received considerable attention due to their convenience and efficiency. These methods have profoundly changed the protocols for the construction of natural products, building blocks for supramolecular chemistry and self-assembly, pharmaceuticals, agrochemicals, and advanced materials on both laboratory and industrial scales.

Nowadays, transition metal-catalysed cross-coupling reactions constitute an important tool for the synthesis and functionalization of several types of heterocyclic compounds, but the field is still wide-open for innovation and will continue to advance as even more versatile transformations are developed. For instance, multicomponent reactions have been used for the synthesis of heterocycles and many strategies have been developed for the construction of highly functionalized heterocycles, but there are also works focused on the direct functionalization of heteroaromatic compounds.

The present Special Issue intends to highlight updated contributions in the construction and functionalisation of heterocyclic compounds and derivatives involving transition metal-catalyzed cross-coupling reactions as the key step. Reviews articles by experts in the field will also be welcome.

Prof. Dr. Artur M. S. Silva
Dr. Maria Manuel Marques
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Metal-catalysis
  • Cross-coupling reactions
  • Transmetallation
  • Mechanisms of cross-coupling reactions
  • Reductive elimination
  • Oxidative addition
  • Heterocycles
  • Synthesis of heterocycles
  • Functionalization of heterocycles
  • Microwave-assisted reactions

Published Papers (8 papers)

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Research

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Open AccessArticle
Design and Synthesis of a Novel Banana-Shaped Functional Molecule via Double Cross-Coupling
Molecules 2019, 24(4), 698; https://doi.org/10.3390/molecules24040698
Received: 4 January 2019 / Revised: 12 February 2019 / Accepted: 12 February 2019 / Published: 15 February 2019
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Abstract
A novel banana-shaped molecule using 2,8-Dimethyl-6H,12H-5,11-methanodibenzo [b,f] [1,5]diazocine (Tröger’s base) as bent-core was synthesized via double Carbon-Carbon cross-coupling reaction. The double Sonogashira cross-coupling reaction was optimized by using Pd(PPh3)2Cl2 as catalyst, CuI [...] Read more.
A novel banana-shaped molecule using 2,8-Dimethyl-6H,12H-5,11-methanodibenzo [b,f] [1,5]diazocine (Tröger’s base) as bent-core was synthesized via double Carbon-Carbon cross-coupling reaction. The double Sonogashira cross-coupling reaction was optimized by using Pd(PPh3)2Cl2 as catalyst, CuI as cocatalyst and diisopropylamine as base in place of triethylamine. The structure of this compound was confirmed by 1H-NMR, 13C-NMR, Fourier transform infrared (FT-IR) spectroscopy and mass spectrometry. Full article
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Open AccessArticle
Synthesis of Pyridazine Derivatives by Suzuki-Miyaura Cross-Coupling Reaction and Evaluation of Their Optical and Electronic Properties through Experimental and Theoretical Studies
Molecules 2018, 23(11), 3014; https://doi.org/10.3390/molecules23113014
Received: 1 October 2018 / Revised: 2 November 2018 / Accepted: 11 November 2018 / Published: 18 November 2018
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Abstract
A series of π-conjugated molecules, based on pyridazine and thiophene heterocycles 3ae, were synthesized using commercially, or readily available, coupling components, through a palladium catalyzed Suzuki-Miyaura cross-coupling reaction. The electron-deficient pyridazine heterocycle was functionalized by a thiophene electron-rich heterocycle at [...] Read more.
A series of π-conjugated molecules, based on pyridazine and thiophene heterocycles 3ae, were synthesized using commercially, or readily available, coupling components, through a palladium catalyzed Suzuki-Miyaura cross-coupling reaction. The electron-deficient pyridazine heterocycle was functionalized by a thiophene electron-rich heterocycle at position six, and different (hetero)aromatic moieties (phenyl, thienyl, furanyl) were functionalized with electron acceptor groups at position three. Density Functional Theory (DFT) calculations were carried out to obtain information on the conformation, electronic structure, electron distribution, dipolar moment, and molecular nonlinear response of the synthesized push-pull pyridazine derivatives. Hyper-Rayleigh scattering in 1,4-dioxane solutions, using a fundamental wavelength of 1064 nm, was used to evaluate their second-order nonlinear optical properties. The thienylpyridazine functionalized with the cyano-phenyl moiety exhibited the largest first hyperpolarizability (β = 175 × 10−30 esu, using the T convention) indicating its potential as a second harmonic generation (SHG) chromophore. Full article
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Open AccessArticle
Zinc (II)-Mediated Selective O-Benzylation of 2-Oxo-1,2-Dihydropyridines Systems
Molecules 2018, 23(7), 1784; https://doi.org/10.3390/molecules23071784
Received: 4 July 2018 / Revised: 16 July 2018 / Accepted: 17 July 2018 / Published: 20 July 2018
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Abstract
The selective O-benzylation of 2-oxo-1,2-dihydropyridines plays a critical role in organic synthesis of natural products and biological active molecules. Herein we report a novel ternary system of ZnO, ZnCl2 and N,N-diisopropylethylamine (DIEA), that is highly effective for selective [...] Read more.
The selective O-benzylation of 2-oxo-1,2-dihydropyridines plays a critical role in organic synthesis of natural products and biological active molecules. Herein we report a novel ternary system of ZnO, ZnCl2 and N,N-diisopropylethylamine (DIEA), that is highly effective for selective O-benzylation of 2-oxo-1,2-dihydropyridines using abundant substituted benzyl halides and related substituted 2-oxo-1,2-dihydropyridines compounds. This process allows access to a variety of O-benzyl products under mild reaction conditions, which are important synthetic intermediates in the protection of functional groups, and represents a new method toward the development for the O-benzylation of 2-oxo-1,2-dihydropyridines. Full article
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Review

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Open AccessReview
Synthesis of Phthalides and α,β-butenolides by Transition Metal-Catalyzed Activation of C—H Bonds
Molecules 2019, 24(4), 824; https://doi.org/10.3390/molecules24040824
Received: 31 January 2019 / Revised: 15 February 2019 / Accepted: 17 February 2019 / Published: 25 February 2019
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Abstract
Phthalides and α,β-butenolides are two related classes of oxygenated heterocycles with a wide range of biological activities. An innovative strategy to prepare these compounds is based on C—H bond functionalization reactions, in which two simple, unfunctionalized molecules are coupled together with cleavage of [...] Read more.
Phthalides and α,β-butenolides are two related classes of oxygenated heterocycles with a wide range of biological activities. An innovative strategy to prepare these compounds is based on C—H bond functionalization reactions, in which two simple, unfunctionalized molecules are coupled together with cleavage of a C—H bond and formation of a C—X bond (X=C or heteroatom). This paper reviews the methods for the synthesis of phthalides and α,β-butenolides by C—H bond functionalization from non-halogenated starting materials. Over 30 methods are reported, mostly developed during the past ten years. Full article
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Open AccessFeature PaperReview
Palladium-Catalysed Synthesis and Transformation of Quinolones
Molecules 2019, 24(2), 228; https://doi.org/10.3390/molecules24020228
Received: 9 December 2018 / Revised: 31 December 2018 / Accepted: 4 January 2019 / Published: 9 January 2019
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Abstract
Palladium-catalysed reactions have had a large impact on synthetic organic chemistry and have found many applications in target-oriented synthesis. Their widespread use in organic synthesis is due to the mild conditions associated with the reactions together with their tolerance of a wide range [...] Read more.
Palladium-catalysed reactions have had a large impact on synthetic organic chemistry and have found many applications in target-oriented synthesis. Their widespread use in organic synthesis is due to the mild conditions associated with the reactions together with their tolerance of a wide range of functional groups. Moreover, these types of reactions allow the rapid construction of complex molecules through multiple bond-forming reactions in a single step, the so-called tandem processes. Pd-catalysed reactions have been applied to the synthesis of a large number of natural products and bioactive compounds, some of them of complex molecular structures. This review article aims to present an overview of the most important Pd-catalysed reactions employed in the synthesis and transformations of quinolin-2(1H)-ones and quinolin-4(1H)-ones. These compounds are widely recognized by their diverse bioactivity, being privileged structures in medicinal chemistry and useful structural moieties for the development of new drug candidates. Furthermore, they hold significant interest due to their host–guest chemistry; applications in chemical, biochemical and environmental analyses and use in the development of new synthetic methods. In some cases, the quinolone formation step cannot be ascribed to a claimed Pd-catalysed reaction but this reaction is crucial to get the appropriate substrate for cyclization into the quinolone. Herein we present and discuss different economical, efficient and selective synthetic strategies to access quinolone-type compounds. Full article
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Open AccessReview
Metal-Catalyzed Cross-Coupling Reactions on Azaindole Synthesis and Functionalization
Molecules 2018, 23(10), 2673; https://doi.org/10.3390/molecules23102673
Received: 28 September 2018 / Revised: 11 October 2018 / Accepted: 13 October 2018 / Published: 17 October 2018
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Abstract
Azaindoles are rare in nature but extremely attractive for drug discovery programs. Azaindoles can be obtained by diverse methods, including those involving metal-catalyzed reactions. This important core has been fascinating the scientific community due to their challenging synthesis and relevant bioactivity. This paper [...] Read more.
Azaindoles are rare in nature but extremely attractive for drug discovery programs. Azaindoles can be obtained by diverse methods, including those involving metal-catalyzed reactions. This important core has been fascinating the scientific community due to their challenging synthesis and relevant bioactivity. This paper highlights the diverse synthetic methodologies developed to date involving metal-catalyzed reaction to attain azaindoles and its functionalization. Full article
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Open AccessReview
The Current Status of Heterogeneous Palladium Catalysed Heck and Suzuki Cross-Coupling Reactions
Molecules 2018, 23(7), 1676; https://doi.org/10.3390/molecules23071676
Received: 31 May 2018 / Revised: 22 June 2018 / Accepted: 23 June 2018 / Published: 10 July 2018
Cited by 4 | PDF Full-text (5830 KB) | HTML Full-text | XML Full-text
Abstract
In the last 30 years, C–C cross coupling reactions have become a reliable technique in organic synthesis due their versatility and efficiency. While drawbacks have been experienced on an industrial scale with the use of homogenous systems, many attempts have been made to [...] Read more.
In the last 30 years, C–C cross coupling reactions have become a reliable technique in organic synthesis due their versatility and efficiency. While drawbacks have been experienced on an industrial scale with the use of homogenous systems, many attempts have been made to facilitate a heterogeneous renaissance. Thus, this review gives an overview of the current status of the use of heterogeneous catalysts particularly in Suzuki and Heck reactions. Most recent developments focus on palladium immobilised or supported on various classes of supports, thus this review highlights and discuss contributions of the last decade. Full article
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Open AccessReview
Cobalt-Catalyzed (Hetero)arylation of Saturated Cyclic Amines with Grignard Reagents
Molecules 2018, 23(6), 1449; https://doi.org/10.3390/molecules23061449
Received: 16 May 2018 / Revised: 6 June 2018 / Accepted: 7 June 2018 / Published: 14 June 2018
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Abstract
(Hetero)aryl substituted saturated cyclic amines are ubiquitous scaffolds in biologically active molecules. Metal-catalyzed cross-couplings between halogeno N-heterocycles and organometallic species are efficient and modular reactions to access these attractive scaffolds. An overview of our work concerning the cobalt-catalyzed arylation of iodo-substituted cyclic [...] Read more.
(Hetero)aryl substituted saturated cyclic amines are ubiquitous scaffolds in biologically active molecules. Metal-catalyzed cross-couplings between halogeno N-heterocycles and organometallic species are efficient and modular reactions to access these attractive scaffolds. An overview of our work concerning the cobalt-catalyzed arylation of iodo-substituted cyclic amines is presented. Full article
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